CN102515744A - A kind of CaCu3Ti4O12 micro-nano fiber and its preparation method - Google Patents
A kind of CaCu3Ti4O12 micro-nano fiber and its preparation method Download PDFInfo
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- CN102515744A CN102515744A CN2011104117909A CN201110411790A CN102515744A CN 102515744 A CN102515744 A CN 102515744A CN 2011104117909 A CN2011104117909 A CN 2011104117909A CN 201110411790 A CN201110411790 A CN 201110411790A CN 102515744 A CN102515744 A CN 102515744A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910002966 CaCu3Ti4O12 Inorganic materials 0.000 title abstract 5
- 239000002121 nanofiber Substances 0.000 title description 6
- 239000000835 fiber Substances 0.000 claims abstract description 77
- 239000010936 titanium Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 24
- 235000019441 ethanol Nutrition 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 238000010041 electrostatic spinning Methods 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 229910004247 CaCu Inorganic materials 0.000 claims description 39
- 238000013019 agitation Methods 0.000 claims description 36
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 16
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 239000005030 aluminium foil Substances 0.000 claims description 12
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 12
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 13
- 238000009987 spinning Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract 4
- 239000012752 auxiliary agent Substances 0.000 abstract 2
- 230000003068 static effect Effects 0.000 abstract 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 abstract 1
- 229910010272 inorganic material Inorganic materials 0.000 abstract 1
- 239000011147 inorganic material Substances 0.000 abstract 1
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical class O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- -1 alkoxy compound Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000005686 electrostatic field Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000011222 crystalline ceramic Substances 0.000 description 1
- 229910002106 crystalline ceramic Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical class [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a CaCu3Ti4O12 micro nano sized fiber and its preparation method, which belongs to the inorganic material technical field. The CaCu3Ti4O12 micro nano sized fiber comprises the elements of Ca, Cu, Ti and O with the mol ratio of 13412, and the diameter is 200-300 nanometers. The preparation method comprises the following steps mixing anhydrous ethyl alcohol, calcium nitrate tetrahydrate and copper acetate monohydrate to obtain a solution A; mixing anhydrous ethanol, butyl titanate and a spinning auxiliary agent to obtain a solution B; slowly adding the solution B in the solution A, and using a static spinning technology to prepare the CaCu3Ti4O12 micro nano sized fiber. The method of the invention can effectively control the hydrolysis process of the raw materials by selecting and adjusting the ratio of raw materials and the spinning auxiliary agent, the obtained static spinning solution possesses spinnability, and the method of the invention provides the novel CaCu3Ti4O12 micro nano sized fiber. The preparation method has the advantages of simple process, mild condition, easy control and wide applicability.
Description
Technical field
the present invention relates to a kind of inorganic fibers technology, are specifically related to a kind of micro-nano level ceramic fiber and preparation method thereof.
Background technology
high dielectric constant materials can be used for the manufacturing of the capacitive device of small volume; For the electron device microminiaturization provides very big possibility; Therefore it has purposes very widely, the important effect of play more and more in microelectronics industry in fields such as microresonator, wave filter, portable phones.
People such as Subramanian (M.A. Subramanian, Dong Li, et al. J. Solid State Chemistry, 2000,151:323-325) found to have the CaCu of perovskite-like structure in 2000
3
Ti
4
O
12
(being abbreviated as CCTO) has very high specific inductivity (generalized case is greater than 10000) in the TR of 100～500K; And in very wide TR; Do not have structural phase transition and ferroelectric phase transition, therefore, this material has broad prospects in the application of electron trade.
are that the one dimension micro-nano level material of representative has particular optical performance, electric property and space geometry structure with the fiber, are the ideal materials that research and development have novel electron transport property, optical characteristics and mechanical property.But, present CaCu
3
Ti
4
O
12
Be confined to existence forms such as ceramic sintered bodies, powder and film, also do not see about CaCu
3
Ti
4
O
12
The report of micro-nano level fiber makes it the limited use in high frontiers such as transmitters.
At present, preparation CaCu
3
Ti
4
O
12
The method of sample mainly is solid sintering process, sol-gel method and pulsed laser deposition.Solid sintering process is prepared into fine and close micro-crystalline ceramic through high temperature solid-phase sintering then through the superfine powder of each component of mechanical milling method preparation; But preparation technology is harsh for this method, has only accurate control, could obtain the stable CaCu of specific inductivity
3
Ti
4
O
12
Pottery.Characteristics such as sol-gel method is the effective ways of preparation even superfine powder, has the purity height, and each component molecular level chemistry evenly, particle size is controlled, equipment is simple.Pulsed laser deposition can the growth in situ high-temperature superconducting thin film, is all having broad application prospects aspect the preparation thin-film material or the material of nanostructure.But also having no small difficulty aspect the higher-quality nano material of preparation, and because search time is shorter, how to be more prone to, to control simply the growth mechanism of formation nanostructure and nanostructure, all need further explore.Above-mentioned three kinds of methods all can't obtain CaCu
3
Ti
4
O
12
Micro-nano level fiber.
in recent years; Electrostatic spinning technique gets more and more people's extensive concerning; It is a kind of method that obtains fiber through high pressure electrostatic; Its core is that charged spinning solution is flowed in electrostatic field and distortion, along with solvent evaporation or melt cooling and solidify, thereby obtains fiber.With data by MoM and MEI, electrostatic spinning has remarkable advantages.For example, the fiber length-to-diameter ratio of preparation is very big, and staple length can reach macro-scale; Preparation condition gentleness, rapid speed, output are bigger, and applicable surface is extensive, and the preparation process is very simple, is to prepare very effective, the easy method of fiber.Before the present invention makes; Chinese invention patent (CN102084044A) discloses the method that a kind of electrostatic spinning through solution is produced inorganic nano-fiber, and this solution comprises that being dissolved in alcohol is metal or semi-metal or the nonmetallic alcoxylates in the solvent system on basis.Solution is prevented from the sequestrant institute stabilization of the hydrolysis of alcoxylates; After homogenizing this solution with mix by gathering (vinyl pyrrolidone) solution in alcohol; Gained solution is transported to electrostatic field then; Carry out electrostatic spinning therein continuously, the result of spinning is the production of organic-inorganic nano fiber, and this fiber is being calcined in air atmosphere under 500～1300 ℃ temperature outside the spinning equipment then.Chinese invention patent " a kind of electrostatic spinning prepares the method for alumina nano fiber " (CN 101982581A) is dissolved in polymkeric substance in the solvent; Again aluminium acetylacetonate is joined in the polymers soln; The preparation spinning solution through electrostatic spinning and sintering processes, obtains alumina nano fiber.Technique scheme provides the fiber of preparation simple oxide, and CaCu
3
Ti
4
O
12
Pottery is made up of by fixed proportion three kinds of metallic elements, in order to the inorganic salt of the alkoxy compound of titanium and calcium and copper correspondence during as raw material, contains crystal water and water-absorbent that itself had in the inorganic salt owing to calcium and copper; To cause metal alkoxide compound hydrolysis and polymerization apace, even produce partial gel, and make the viscosity of spinning solution be the geometricprogression rising; Can carry out the scope of electrostatic spinning head and shoulders above; This phenomenon is as easy as rolling off a log occur in spinning before, brought difficulty to electrostatic spinning process, even electrostatic spinning can't be carried out; Therefore, do not see that at present CaCu is arranged
3
Ti
4
O
12
The use of nanofiber in the prior art, is not seen about electrospinning process to prepare CaCu yet
3
Ti
4
O
12
The report of micro-nano level fiber.
Summary of the invention
In order to overcome the deficiency that prior art exists, the object of the present invention is to provide a kind of CaCu
3
Ti
4
O
12
Micro-nano level fiber, and a kind of technology is simple, mild condition, widely applicable CaCu
3
Ti
4
O
12
Micro-nano level fiber preparation method.
Realize that the technical scheme that the object of the invention adopted provides a kind of CaCu
3
Ti
4
O
12
Micro-nano level fiber, it comprises Elements C a, Cu, Ti and O, they be 1:3:4:12 in molar ratio; , Fibre diameter is 200～300 nanometers.
A kind of CaCu
3
Ti
4
O
12
Micro-nano level fiber preparation method comprises the steps:
1, under agitation condition, by weight, 100～200 parts of absolute ethyl alcohols, 1～5 part of calcium nitrate tetrahydrate and 2～10 part of one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 1～5 hour under 20～50 ℃ temperature condition, obtains solution A;
2, under agitation condition; By weight; 5～30 parts of Vinylpyrrolidone polymers, 100～200 parts of absolute ethyl alcohols, 3～15 parts of spin finish aids and 3～15 parts of butyl(tetra)titanates are joined in the reaction vessel, and isothermal reaction is 1～3 hour under 20～50 ℃ temperature condition, obtains solution B;
3, under agitation condition, solution B slowly is added drop-wise in the solution A, obtain electrostatic spinning solution;
4, adopt electrostatic spinning process to obtain fiber;
5, the fiber that electrostatic spinning is obtained 50～70 ℃ dry 12～18 hours down, be heated to 900～1000 ℃ with 5～10 ℃/minute temperature rise rate again, and constant temperature 2～5 hours, obtain CaCu
3
Ti
4
O
12
Micro-nano level fiber.
described spin finish aid is acetate, TMAH, or a kind of in the Pottasium Hydroxide.
electrostatic spinning process is 15～30 kilovolts of voltages, solidifies 5～15 centimetres of distances, and receiving trap is an aluminium foil.
Compared with prior art, the beneficial effect that has of the present invention is: a kind of CaCu is provided
3
Ti
4
O
12
Fiber, it is CaCu
3
Ti
4
O
12
A kind of new existence form.The present invention controls the hydrolytic process of raw material effectively through proportioning, addition manner and the spin finish aid of each experimental raw of adjustment, and the electrostatic spinning process is carried out smoothly.The preparation method who is proposed has that technology is simple, mild condition, be easy to control, widely applicable characteristics.
Description of drawings
Fig. 1 is the CaCu that the embodiment of the invention 1 provides
3
Ti
4
O
12
The SEM figure of micro-nano level fiber;
Fig. 2 is the CaCu that the embodiment of the invention 1 provides
3
Ti
4
O
12
The XRD figure of micro-nano level fiber;
Fig. 3 is the CaCu that the embodiment of the invention 5 provides
3
Ti
4
O
12
The SEM figure of micro-nano level fiber;
Fig. 4 is the CaCu that the embodiment of the invention 5 provides
3
Ti
4
O
12
The XRD figure of micro-nano level fiber;
Fig. 5 is the CaCu that the embodiment of the invention 8 provides
3
Ti
4
O
12
The SEM figure of micro-nano level fiber;
Fig. 6 is the CaCu that the embodiment of the invention 8 provides
3
Ti
4
O
12
The XRD figure of micro-nano level fiber.
Embodiment
further describe technical scheme of the present invention below in conjunction with accompanying drawing and embodiment.
Embodiment 1
1, under agitation condition, 10 milliliters of absolute ethyl alcohols, 1.04 gram calcium nitrate tetrahydrates and 2.63 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 2 hours under 30 ℃ temperature condition, obtains solution A;
2, under agitation condition, 1.5 gram Vinylpyrrolidone polymers, 10 milliliters of absolute ethyl alcohols, 3 milliliters of acetate and 6 milliliters of butyl(tetra)titanates are joined in the reaction vessel, isothermal reaction is 1 hour under 30 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 100 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 16.50 kilovolts, and sample rate is 6.5 milliliters/hour, and solidifying distance is 12 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 3 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 60 ℃ dry 15 hours down, be heated to 900 ℃ with 5 ℃/minute temperature rise rate then, and constant temperature 3 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Referring to accompanying drawing 1 is the CaCu that embodiment 1 provides
3
Ti
4
O
12
The SEM figure of fiber can find out CaCu
3
Ti
4
O
12
For fibers form exists, diameter is about 200～300 nanometers.
Referring to accompanying drawing 2 are present embodiment CaCu
3
Ti
4
O
12
The XRD figure of fiber therefrom can be found out CaCu
3
Ti
4
O
12
The structure of fiber is pure CaCu
3
Ti
4
O
12
Phase.
Embodiment 2
1, under agitation condition, 15 milliliters of absolute ethyl alcohols, 1.04 gram calcium nitrate tetrahydrates and 2.63 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 3 hours under 45 ℃ temperature condition, obtains solution A;
2, under agitation condition, 2.5 gram Vinylpyrrolidone polymers, 15 milliliters of absolute ethyl alcohol 1.5 gram TMAHs and 6 milliliters of butyl(tetra)titanates are joined in the reaction vessel, isothermal reaction is 3 hours under 45 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 200 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 19.50 kilovolts, and sample rate is 8.5 milliliters/hour, and solidifying distance is 15 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 70 ℃ dry 18 hours down, be heated to 950 ℃ with 10 ℃/minute temperature rise rate then, and constant temperature 5 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
1, under agitation condition, 20 milliliters of absolute ethyl alcohols, 2.08 gram calcium nitrate tetrahydrates and 5.26 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 1 hour under 50 ℃ temperature condition, obtains solution A;
2, under agitation condition, 3 gram Vinylpyrrolidone polymers, 20 milliliters of absolute ethyl alcohol 3 gram TMAHs and 12 milliliters of butyl(tetra)titanates are joined in the reaction vessel, isothermal reaction is 1 hour under 50 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 150 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 23.50 kilovolts, and sample rate is 9.5 milliliters/hour, and solidifying distance is 15 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 50 ℃ dry 12 hours down, be heated to 1000 ℃ with 7 ℃/minute temperature rise rate then, and constant temperature 2 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Embodiment 4
1, under agitation condition, 15 milliliters of absolute ethyl alcohols, 1.56 gram calcium nitrate tetrahydrates and 3.95 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 1 hour under 20 ℃ temperature condition, obtains solution A;
2, under agitation condition, 1.9 gram Vinylpyrrolidone polymers, 18 milliliters of absolute ethyl alcohol 1 gram Pottasium Hydroxide and 9 milliliters of butyl(tetra)titanates are joined in the reaction vessel, isothermal reaction is 1 hour under 20 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 200 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 27.50 kilovolts, and sample rate is 8.5 milliliters/hour, and solidifying distance is 12 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 70 ℃ dry 18 hours down, be heated to 1000 ℃ with 9 ℃/minute temperature rise rate then, and constant temperature 3 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Embodiment 5
1, under agitation condition, 20 milliliters of absolute ethyl alcohols, 1.56 gram calcium nitrate tetrahydrates and 3.95 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 1 hour under 50 ℃ temperature condition, obtains solution A;
2, under agitation condition, 3 gram Vinylpyrrolidone polymers, 20 milliliters of absolute ethyl alcohol 1.5 gram Pottasium Hydroxide and 9 milliliters of butyl(tetra)titanates are joined in the reaction vessel, isothermal reaction is 3 hours under 20 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 200 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 30 kilovolts, and sample rate is 10 milliliters/hour, and solidifying distance is 15 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 70 ℃ dry 18 hours down, be heated to 1000 ℃ with 5 ℃/minute temperature rise rate then, and constant temperature 3 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Referring to accompanying drawing 3 and 4 is respectively the CaCu that present embodiment provides
3
Ti
4
O
12
The SEM figure and the XRD figure of fiber can be found out CaCu
3
Ti
4
O
12
For fibers form exists and is pure CaCu
3
Ti
4
O
12
Phase, diameter are about 200～300 nanometers.
Embodiment 6
1, under agitation condition, 20 milliliters of absolute ethyl alcohols, 1.56 gram calcium nitrate tetrahydrates and 3.95 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 5 hours under 20 ℃ temperature condition, obtains solution A;
2, under agitation condition, 1.3 gram Vinylpyrrolidone polymers, 20 milliliters of absolute ethyl alcohol 0.5 gram Pottasium Hydroxide and 9 milliliters of butyl(tetra)titanates are joined in the reaction vessel, isothermal reaction is 3 hours under 20 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 200 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 15 kilovolts, and sample rate is 1 milliliter/hour, and solidifying distance is 5 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 5 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 50 ℃ dry 12 hours down, be heated to 900 ℃ with 10 ℃/minute temperature rise rate then, and constant temperature 5 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Embodiment 7
1, under agitation condition, 10 milliliters of absolute ethyl alcohols, 0.78 gram calcium nitrate tetrahydrate and 1.98 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 5 hours under 20 ℃ temperature condition, obtains solution A;
2, under agitation condition, 0.5 gram Vinylpyrrolidone polymer, 0.8 milliliter of acetate of 10 milliliters of absolute ethyl alcohols and 4.5 milliliters of butyl(tetra)titanates are joined in the reaction vessel, isothermal reaction is 3 hours under 20 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 100 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 15 kilovolts, and sample rate is 2.3 milliliters/hour, and solidifying distance is 10 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 5 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 60 ℃ dry 12 hours down, be heated to 950 ℃ with 5 ℃/minute temperature rise rate then, and constant temperature 2 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
1, under agitation condition, 20 milliliters of absolute ethyl alcohols, 2.08 gram calcium nitrate tetrahydrates and 5.26 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 1 hour under 30 ℃ temperature condition, obtains solution A;
2, under agitation condition, 2.5 gram Vinylpyrrolidone polymers, 15 milliliters of absolute ethyl alcohol 1.5 gram TMAHs and 12 milliliters of butyl(tetra)titanates are joined in the reaction vessel, isothermal reaction is 1 hour under 50 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 150 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 23.50 kilovolts, and sample rate is 9.5 milliliters/hour, and solidifying distance is 15 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 50 ℃ dry 12 hours down, be heated to 950 ℃ with 5 ℃/minute temperature rise rate then, and constant temperature 2 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Referring to accompanying drawing 5 and 6, be respectively the CaCu that present embodiment provides
3
Ti
4
O
12
The SEM figure and the XRD figure of fiber can be found out CaCu
3
Ti
4
O
12
For fibers form exists and is pure CaCu
3
Ti
4
O
12
Phase, diameter are about 200～300 nanometers.
Embodiment 9
1, under agitation condition, 18 milliliters of absolute ethyl alcohols, 1.04 gram calcium nitrate tetrahydrates and 2.63 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 3 hours under 35 ℃ temperature condition, obtains solution A;
2, under agitation condition, 2.1 gram Vinylpyrrolidone polymers, 18 milliliters of absolute ethyl alcohol 1.8 gram TMAHs and 6 milliliters of butyl(tetra)titanates are joined in the reaction vessel, isothermal reaction is 3 hours under 45 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 100 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 22.50 kilovolts, and sample rate is 7.5 milliliters/hour, and solidifying distance is 17 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 70 ℃ dry 18 hours down, be heated to 900 ℃ with 10 ℃/minute temperature rise rate then, and constant temperature 4 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Embodiment 10
1, under agitation condition, 13 milliliters of absolute ethyl alcohols, 1.04 gram calcium nitrate tetrahydrates and 2.63 grams, one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 3 hours under 45 ℃ temperature condition, obtains solution A;
2, under agitation condition, 1.9 gram Vinylpyrrolidone polymers, 13 milliliters of absolute ethyl alcohol 1.1 gram TMAHs and 6 milliliters of butyl(tetra)titanates are joined in the reaction vessel, isothermal reaction is 3 hours under 45 ℃ temperature condition, obtains solution B;
3, under agitation condition, the solution B that makes in the step 2 all slowly is added drop-wise in the solution A, rate of addition obtains solution C for per hour dripping 200 milliliters;
4, solution C is carried out electrostatic spinning, the voltage that electrostatic spinning uses is 21.50 kilovolts, and sample rate is 9.5 milliliters/hour, and solidifying distance is 16 centimetres, and receiving trap is an aluminium foil, and the electrostatic spinning time is 2 hours, obtains corresponding fiber;
5, the fiber that electrostatic spinning is obtained 65 ℃ dry 15 hours down, be heated to 950 ℃ with 5 ℃/minute temperature rise rate then, and constant temperature 4 hours, obtain novel C aCu
3
Ti
4
O
12
Fiber.
Claims (4)
1. CaCu
3Ti
4O
12Micro-nano level fiber is characterized in that: it comprises Elements C a, Cu, Ti and O, and they are 1:3:4:12 in molar ratio; , Fibre diameter is 200～300 nanometers.
2. a kind of CaCu as claimed in claim 1
3Ti
4O
12Micro-nano level fiber preparation method is characterized in that comprising the steps:
(1) under agitation condition, by weight, 100～200 parts of absolute ethyl alcohols, 1～5 part of calcium nitrate tetrahydrate and 2～10 part of one hydrated copper acetate are joined in the reaction vessel, isothermal reaction is 1～5 hour under 20～50 ℃ temperature condition, obtains solution A;
(2) under agitation condition; By weight; 5～30 parts of Vinylpyrrolidone polymers, 100～200 parts of absolute ethyl alcohols, 3～15 parts of spin finish aids and 3～15 parts of butyl(tetra)titanates are joined in the reaction vessel, and isothermal reaction is 1～3 hour under 20～50 ℃ temperature condition, obtains solution B;
(3) under agitation condition, solution B slowly is added drop-wise in the solution A, obtain electrostatic spinning solution;
(4) adopt electrostatic spinning process to obtain fiber;
(5) fiber that electrostatic spinning is obtained 50～70 ℃ dry 12～18 hours down, be heated to 900～1000 ℃ with 5～10 ℃/minute temperature rise rate again, and constant temperature 2～5 hours, obtain CaCu
3Ti
4O
12Micro-nano level fiber.
3. CaCu according to claim 2
3Ti
4O
12Micro-nano level fiber preparation method is characterized in that: described spin finish aid is acetate, TMAH, or a kind of in the Pottasium Hydroxide.
4. CaCu according to claim 2
3Ti
4O
12Micro-nano level fiber preparation method is characterized in that: electrostatic spinning process is 15～30 kilovolts of voltages, solidifies 5～15 centimetres of distances, and receiving trap is an aluminium foil.
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